CN113061080A - Micro-interface reaction system and method for preparing butyraldehyde by propylene carbonylation - Google Patents
Micro-interface reaction system and method for preparing butyraldehyde by propylene carbonylation Download PDFInfo
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- CN113061080A CN113061080A CN202110354304.8A CN202110354304A CN113061080A CN 113061080 A CN113061080 A CN 113061080A CN 202110354304 A CN202110354304 A CN 202110354304A CN 113061080 A CN113061080 A CN 113061080A
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 47
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 26
- 230000006315 carbonylation Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 12
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 238000003860 storage Methods 0.000 claims abstract description 50
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 83
- 239000003054 catalyst Substances 0.000 claims description 31
- 239000007791 liquid phase Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 19
- 238000010406 interfacial reaction Methods 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention provides a micro-interface reaction system for preparing butyraldehyde by propylene carbonylation, which comprises: a solvent storage tank, a reactor and a gas-liquid separator; the side wall of the reactor is sequentially provided with a propylene inlet and a synthesis gas inlet from top to bottom; the bottom of the reactor is provided with a solvent inlet which is connected with the solvent storage tank; a demister is arranged between the reactor and the gas-liquid separator; demisting the product in the reactor by the demister, and then flowing into the gas-liquid separator for gas-liquid separation; a first micro-interface generator and a second micro-interface generator are arranged in the reactor; the first micro-interface generator is connected with the propylene inlet and is used for dispersing and breaking propylene into micro-bubbles. The micro-interface reaction system greatly reduces the reaction temperature and pressure required by propylene carbonylation, has low energy consumption, low cost, high safety, less side reaction and high n-butyraldehyde yield, and is worthy of wide popularization and application.
Description
Technical Field
The invention relates to the field of propylene hydroxylation reaction preparation, in particular to a micro-interface reaction system and a micro-interface reaction method for preparing butyraldehyde by propylene carbonylation.
Background
Butanol and octanol are important raw materials for synthesizing fine chemical products, and the preparation of n-butyl aldehyde is the most important ring in the preparation process of butanol and octanol. In the prior art, the generation of butyraldehyde mainly takes synthesis gas and propylene as raw materials, a rhodium carbonyl/triphenylphosphine complex as a catalyst, mixed butyraldehyde is generated by reaction, and a butyraldehyde mixture is obtained by further rectification after the catalyst is separated; however, in the prior art, in the oxo reaction of the synthesis gas and the propylene under the action of the catalyst, the synthesis gas, the propylene and the catalyst cannot be fully mixed in the oxo reactor, so that the reaction efficiency is low and the energy consumption is high in the reaction process, and the yield of n-butyl aldehyde in the generated butyraldehyde mixture is low and the service life of the catalyst is short due to the overhigh reaction temperature, so that the production cost of an enterprise is increased.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a micro-interface reaction system for preparing butyraldehyde by propylene carbonylation, which, on one hand, is to respectively disperse and break propane and synthesis gas into micro bubbles by respectively arranging a first micro-interface generator and a second micro-interface generator inside a reactor, thereby increasing phase interface area, fully satisfying mass transfer space, increasing the retention time of gas in liquid phase, improving the solubility of propane and synthesis gas, reducing energy consumption and improving reaction efficiency; on the other hand, the operation temperature and pressure in the reactor are reduced, and the safety and stability of the whole reaction system are improved.
The second purpose of the invention is to provide a reaction method for preparing butyraldehyde by adopting the micro-interface reaction system for preparing butyraldehyde by propylene hydroxylation, the reaction method is simple and convenient to operate, the obtained n-butyraldehyde is high in purity and product quality, the energy consumption is reduced, and the reaction effect is better than that of the existing process.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a micro-interface reaction system for preparing butyraldehyde by propylene carbonylation, which comprises: the system comprises a solvent storage tank, a reactor, a gas-liquid separator, a propylene storage tank, a carbon monoxide storage tank, a hydrogen storage tank, a propylene pipeline and a synthesis gas pipeline; the side wall of the reactor is sequentially provided with a propylene inlet and a synthesis gas inlet from top to bottom; the bottom of the reactor is provided with a solvent inlet which is connected with the solvent storage tank; a demister is arranged between the reactor and the gas-liquid separator; demisting the product in the reactor by the demister, and then flowing into the gas-liquid separator for gas-liquid separation;
a first micro-interface generator and a second micro-interface generator are arranged in the reactor; the first micro-interface generator is connected with the propylene inlet and is used for dispersing and breaking propylene into micro-bubbles; the second micro-interface generator is connected with the synthesis gas inlet and is used for dispersing and breaking the synthesis gas into micro-bubbles;
the propylene inlet is connected with the propylene storage tank through the propylene pipeline; the carbon monoxide storage tank and the hydrogen storage tank are connected in parallel, and are both connected with the synthesis gas inlet through the synthesis gas pipeline; the propylene pipeline and the synthesis gas pipeline are respectively provided with a pre-disperser used for pre-dispersing and crushing gas into bubbles; the pre-disperser comprises a gas phase main path and a liquid phase branch path; the liquid phase branch is connected with the solvent storage tank, and the solvent in the solvent storage tank enters the gas phase main path through the liquid phase branch and is mixed with the gas in the gas phase main path to form bubbles;
an ejector for ejecting catalyst is arranged on the inner side wall of the reactor, and an ejection port of the ejector faces to a position between the first micro interface generator and the second micro interface generator; the ejector is connected with a catalyst storage tank.
In the prior art, the generation of butyraldehyde mainly takes synthesis gas and propylene as raw materials, a rhodium carbonyl/triphenylphosphine complex as a catalyst, mixed butyraldehyde is generated by reaction, the catalyst is separated, then, the mixture is further rectified to obtain a butyraldehyde mixture, and then, the mixture is subjected to isomer separation to obtain n-butyraldehyde; however, in the prior art, in the oxo reaction of the synthesis gas and the propylene under the action of the catalyst, the synthesis gas, the propylene and the catalyst cannot be fully mixed in the oxo reactor, so that the reaction efficiency is low, the energy consumption is high, the requirements on temperature and pressure are high, the yield of n-butyraldehyde in the generated butyraldehyde mixture is low, and the production cost of an enterprise is increased.
In order to solve the technical problems, the invention provides a micro-interface reaction system for preparing butyraldehyde by propylene carbonylation, which is characterized in that a first micro-interface generator and a second micro-interface generator are arranged in a reactor to respectively disperse and crush propylene and synthesis gas, so that the mass transfer effect is improved, the mass transfer rate is greatly improved, and the temperature and pressure required by the reaction are reduced; through set up the disperser in advance on propylene pipeline and synthetic gas pipeline, break into big bubble with gas earlier before dispersing into the microbubble, little interfacial generator breaks into the microbubble with these big bubbles again, has improved microbubble generation efficiency.
Preferably, the first micro-interface generator is arranged right above the second micro-interface generator, and the first micro-interface generator is opposite to the outlet of the second micro-interface generator. The two micro-interface generators are opposite, so that a hedging effect can be achieved, and gas distribution is promoted.
Preferably, the first micro-interface generator is a hydraulic micro-interface generator, and the second micro-interface generator is a pneumatic micro-interface generator.
Preferably, a screen is arranged at the outlet of the first micro-interface generator, and a guide disc is arranged at the outlet of the second micro-interface generator. The screen and the guide disc are arranged to promote the generated micro bubbles to be further distributed and improve the reaction efficiency.
Preferably, the guide disc is conical; a plurality of guide holes are uniformly distributed on the guide disc. Further, the guide curve of the guide disc is any one of a hyperbolic curve, a parabolic curve, two broken lines and a logarithmic curve.
Preferably, the ejector is of a semicircular shape, the ejector is connected with an ejection head, and the ejection head is uniformly distributed on the semicircular surface of the ejector. The catalyst is dispersed in the reactor by spraying, so that the reaction effect can be improved.
The reactor is internally provided with a first micro-interface generator and a second micro-interface generator respectively, wherein the first micro-interface generator is connected with a propylene inlet, the second micro-interface generator is connected with a synthesis gas inlet, during reaction, a solvent is firstly introduced into the reactor through a solvent inlet, and the liquid level of the solvent is higher than that of the first micro-interface generator. The method comprises the steps that propylene is dispersed into large bubbles through a pre-disperser and then further dispersed into micron-sized micro-bubbles through a first micro-interface generator, synthetic gas is dispersed into large bubbles through the pre-disperser and then further dispersed into micron-sized micro-bubbles through a second micro-interface generator, a solute provides a liquid phase medium for the dispersion and the crushing of the synthetic gas and the large bubbles, and a catalyst is sprayed between the first micro-interface generator and the second micro-interface generator through an ejector to catalyze the carbonylation reaction of the propylene. Demisting the reaction product by a demister, and then feeding the demisted reaction product into a gas-liquid separator.
It should be noted that, in the present invention, the first micro-interface generator is disposed above the second micro-interface generator, and correspondingly, the propylene inlet is disposed above the syngas inlet, because the syngas needs to be synthesized in advance, and the raw materials are flammable and explosive gases, so as to improve the safety of the reactor, the position of the gas inlet is set to be lower as much as possible, and meanwhile, because the gas inlet is more likely to flow towards the top of the reactor after entering the reactor, the first micro-interface generator for breaking propylene is disposed at the upper portion, and the second micro-interface generator for breaking syngas is disposed at the lower portion, such an arrangement manner also fully considers various factors such as safety, reaction efficiency, and the like.
The outlets of the first micro interface generator and the second micro interface generator are opposite, micro bubbles are uniformly distributed through gas hedging, the screen is arranged at the outlet of the first micro interface generator, the guide disc is arranged at the outlet of the second micro interface generator, so that the distribution of the bubbles is improved, and the guide disc is provided with a plurality of guide holes, so that the movement direction of the bubbles can be changed, and the uniform distribution of the bubbles is promoted. The utilization ratio of each microbubble is improved, and the condition that the microbubbles are disordered is avoided, so that the reaction is not favorably carried out smoothly. Especially the arrangement of the second micro-interface generator in the position of engagement with the guide disc is a matter of practice.
In addition, the invention improves the contact between the catalyst and the raw material bubbles by injecting the catalyst between the first micro-interface generator and the second micro-interface generator, in particular, a plurality of injection heads are connected on the injector, each injection head is equivalent to a micro-channel, and the interaction with the gas-phase raw material is strengthened by performing multi-channel arrangement and spraying the liquid-phase catalyst in an injection mode. Therefore, the invention improves the dispersing effect on gas and the application effect of the micro-interface generator by combining the pre-disperser and the micro-interface generator.
It will be appreciated by those skilled in the art that the micro-interface generator used in the present invention is described in the prior patents of the present inventor, such as the patents of application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN 207581700U. The detailed structure and operation principle of the micro bubble generator (i.e. micro interface generator) is described in detail in the prior patent CN201610641119.6, which describes that "the micro bubble generator comprises a body and a secondary crushing member, wherein the body is provided with a cavity, the body is provided with an inlet communicated with the cavity, the opposite first end and second end of the cavity are both open, and the cross-sectional area of the cavity decreases from the middle of the cavity to the first end and second end of the cavity; the secondary crushing member is disposed at least one of the first end and the second end of the cavity, a portion of the secondary crushing member is disposed within the cavity, and an annular passage is formed between the secondary crushing member and the through holes open at both ends of the cavity. The micron bubble generator also comprises an air inlet pipe and a liquid inlet pipe. "the specific working principle of the structure disclosed in the application document is as follows: liquid enters the micro-bubble generator tangentially through the liquid inlet pipe, and gas is rotated at a super high speed and cut to break gas bubbles into micro-bubbles at a micron level, so that the mass transfer area between a liquid phase and a gas phase is increased, and the micro-bubble generator in the patent belongs to a pneumatic micro-interface generator.
In addition, the first patent 201610641251.7 describes that the primary bubble breaker has a circulation liquid inlet, a circulation gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed inlet with the gas-liquid mixture outlet, which indicates that the bubble breakers all need to be mixed with gas and liquid, and in addition, as can be seen from the following drawings, the primary bubble breaker mainly uses the circulation liquid as power, so that the primary bubble breaker belongs to a hydraulic micro-interface generator, and the secondary bubble breaker simultaneously introduces the gas-liquid mixture into an elliptical rotating ball for rotation, thereby realizing bubble breaking in the rotating process, so that the secondary bubble breaker actually belongs to a gas-liquid linkage micro-interface generator. In fact, the micro-interface generator is a specific form of the micro-interface generator, whether it is a hydraulic micro-interface generator or a gas-liquid linkage micro-interface generator, however, the micro-interface generator adopted in the present invention is not limited to the above forms, and the specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can adopt.
Furthermore, the prior patent 201710766435.0 states that the principle of the bubble breaker is that high-speed jet flows are used to achieve mutual collision of gases, and also states that the bubble breaker can be used in a micro-interface strengthening reactor to verify the correlation between the bubble breaker and the micro-interface generator; moreover, in the prior patent CN106187660, there is a related description on the specific structure of the bubble breaker, see paragraphs [0031] to [0041] in the specification, and the accompanying drawings, which illustrate the specific working principle of the bubble breaker S-2 in detail, the top of the bubble breaker is a liquid phase inlet, and the side of the bubble breaker is a gas phase inlet, and the liquid phase coming from the top provides the entrainment power, so as to achieve the effect of breaking into ultra-fine bubbles, and in the accompanying drawings, the bubble breaker is also seen to be of a tapered structure, and the diameter of the upper part is larger than that of the lower part, and also for better providing the entrainment power for the liquid phase.
Since the micro-interface generator was just developed in the early stage of the prior patent application, the micro-interface generator was named as a micro-bubble generator (CN201610641119.6), a bubble breaker (201710766435.0) and the like in the early stage, and is named as a micro-interface generator in the later stage along with the continuous technical improvement, and the micro-interface generator in the present invention is equivalent to the micro-bubble generator, the bubble breaker and the like in the prior art, and has different names. In summary, the micro-interface generator of the present invention belongs to the prior art.
Preferably, the top of the reactor is connected with a first condenser; and a non-condensable gas outlet of the first condenser is connected with a combustion system, and a condensate outlet of the first condenser is connected with the reactor. Tail gas at the top of the reactor is condensed by a first condenser, high boiling point substances such as n-butyl aldehyde/iso-butyl aldehyde and the like are condensed into liquid and return to the reactor, and non-condensable gases such as nitrogen, hydrogen, propane, carbon monoxide and the like enter a combustion system to be combusted and removed.
Preferably, a second condenser is arranged between the demister and the gas-liquid separator; and a material outlet of the gas-liquid separator is sequentially connected with an isomerate separating tower, a rectifying tower and a n-butyl aldehyde storage tank. After the demister demists, the material flows into the gas-liquid separator through the condensation of the second condenser.
Preferably, the outlet of the gas-liquid separator is connected with a third condenser; a part of the material separated by the gas-liquid separator flows back to the reactor through the third condenser; the other part flows into the isomerate separating tower. Furthermore, a circulating pump is arranged at the outlet of the gas-liquid separator, liquid-phase material flow at the bottom of the gas-liquid separator enters the circulating pump to increase the pressure, one part of the material at the outlet of the circulating pump flows into the isomerate separating tower as a crude product, and the other part of the material is cooled to about 80 ℃ by a third condenser and returns to the micro-interface generator in the reactor to continuously participate in the reaction.
Preferably, a reboiler is arranged between the rectifying tower and the n-butyraldehyde storage tank, the product rectified by the rectifying tower is divided into a gas-phase material flow and a liquid-phase material flow in the reboiler, the liquid-phase material flow directly flows into the n-butyraldehyde storage tank, and the gas-phase material flow returns to the rectifying tower.
The invention also provides a reaction method of the micro-interface reaction system for preparing butyraldehyde by propylene carbonylation, which comprises the following steps:
respectively dispersing and crushing propylene and synthesis gas through a micro interface, mixing the propylene and the synthesis gas with a catalyst, carrying out hydroxyl synthesis reaction, carrying out defoaming condensation gas-liquid separation to obtain a crude product, separating n-butyl aldehyde and iso-butyl aldehyde from the crude product, and carrying out rectification and purification to obtain the n-butyl aldehyde.
Preferably, the hydroxyl synthesis reaction temperature is 85-90 ℃, and the pressure is 1.1-1.8 MPa; preferably, the catalyst is a rhodium catalyst.
Specifically, the reaction method comprises the steps of respectively dispersing and crushing propylene and synthesis gas by arranging the first micro-interface generator and the second micro-interface generator in the reactor, so that the propylene and the synthesis gas are crushed into micro-bubbles with the diameter of more than or equal to 1 mu m and less than 1mm before the carbonylation reaction, the mass transfer area of a phase boundary is increased, the solubility of the propylene and the synthesis gas in a solvent is improved, the reaction pressure is reduced, and the reaction efficiency is improved.
The n-butanol product obtained by the reaction method has good quality and high yield. And the preparation method has the advantages of low reaction temperature, greatly reduced pressure and remarkably reduced cost.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the reaction system, the outlets of the first micro-interface generator and the second micro-interface generator are opposite, so that micro-bubbles are uniformly distributed through gas hedging;
(2) the distribution of bubbles is further improved by arranging a screen at the outlet of the first micro-interface generator and arranging a guide disc at the outlet of the second micro-interface generator;
(3) the guide disc is provided with a plurality of guide holes, so that the movement direction of the bubbles can be changed, and the uniform distribution of the bubbles is promoted;
(4) by injecting the catalyst between the first and second micro-interface generators, the contact of the catalyst with the feedstock bubbles is enhanced, enhancing the interaction with the gas phase feedstock.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic structural diagram of a micro-interfacial reaction system for producing butyraldehyde by carbonylation of propylene according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an ejector of a micro-interfacial reaction system and method for producing butyraldehyde by carbonylation of propylene according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a pre-disperser of a micro-interfacial reaction system and a method for producing butyraldehyde by carbonylation of propylene according to an embodiment of the present invention.
Description of the drawings:
10-a reactor; 101-solvent inlet;
102-a syngas inlet; 103-propylene inlet;
104-a first micro-interface generator; 105-a screen;
106-an ejector; 107-guide disc;
108-a second micro-interface generator; 109-an ejection head;
20-a demister; 30-a second condenser;
40-a gas-liquid separator; 50-a circulating pump;
60-a third condenser; 70-an isomerate separation column;
80-a fourth condenser; 90-a rectifying tower;
100-a reboiler; 110-n-butyraldehyde storage tank;
120-solvent storage tank; 130-a carbon monoxide storage tank;
140-a hydrogen storage tank; 150-a propylene storage tank;
160-predispersor; 1601 — a gas phase main path;
1602-liquid phase branch;
170-a combustion system; 180-a first condenser;
190-a catalyst storage tank; a 200-propylene line;
210-syngas line.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Examples
Referring to fig. 1-3, this example provides a micro-interfacial reaction system for the carbonylation of propylene to produce butyraldehyde comprising: a solvent storage tank 120, a reactor 10, a gas-liquid separator 40, a propylene storage tank 150, a carbon monoxide storage tank 130, a hydrogen storage tank 140, a propylene pipeline 200 and a synthesis gas pipeline 210; the side wall of the reactor 10 is provided with a propylene inlet 103 and a synthesis gas inlet 102 from top to bottom in sequence; the bottom of the reactor 10 is provided with a solvent inlet 101, and the solvent inlet 101 is connected with a solvent storage tank 120; a demister 20 is arranged between the reactor 10 and the gas-liquid separator 40; the product in the reactor 10 is demisted by the demister 20 and flows into the gas-liquid separator 40 for gas-liquid separation.
The outlet of the gas-liquid separator 40 is connected with a third condenser 60; a part of the material separated by the gas-liquid separator 40 flows back to the reactor 10 through the third condenser 60; another portion flows into the isomerate separation column 70. Specifically, a circulating pump 50 is disposed at an outlet of the gas-liquid separator 40, a liquid-phase material flow at the bottom of the gas-liquid separator 40 enters the circulating pump 50 to increase the pressure, a part of the material at the outlet of the circulating pump 50 flows into the isomer separation tower 70 as a crude product, and the other part of the material is cooled to about 80 ℃ by the third condenser 60 and then returns to the micro-interface generator in the reactor 10 to continuously participate in the reaction.
A second condenser 30 is arranged between the demister 20 and the gas-liquid separator 40; the material outlet of the gas-liquid separator 40 is connected in sequence with an isomer separating column 70, a rectifying column 90 and a n-butyraldehyde storage tank 110. After the demister 20 demists, the material is condensed by the second condenser 30 and flows into the gas-liquid separator 40.
The isomerate separating column 70 is provided at the top with a fourth condenser 80.
A reboiler 100 is arranged between the rectifying tower 90 and the n-butyraldehyde storage tank 110, the product rectified by the rectifying tower 90 is divided into a gas phase material flow and a liquid phase material flow in the reboiler 100, the liquid phase material flow directly flows into the n-butyraldehyde storage tank 110, and the gas phase material flow returns to the rectifying tower 90.
In this embodiment, the propylene inlet 103 is connected to the propylene storage tank 150 through a propylene line 200; the carbon monoxide storage tank 130 and the hydrogen storage tank 140 are connected in parallel, and the carbon monoxide storage tank 130 and the hydrogen storage tank 140 are both connected with the synthesis gas inlet 102 through the synthesis gas pipeline 210; the propylene pipeline 200 and the synthesis gas pipeline 210 are both provided with a pre-disperser 160 for pre-dispersing and crushing gas into bubbles; as shown in fig. 3, pre-disperser 160 comprises a main vapor phase path 1601 and a branch liquid phase path 1602; the liquid phase branch 1602 is connected to the solvent storage tank 120, and the solvent in the solvent storage tank 120 enters the gas phase main path 1601 through the liquid phase branch 1602 and is mixed with the gas in the gas phase main path 1601 to form bubbles;
in this embodiment, the reactor 10 is internally provided with a first micro-interface generator 104 and a second micro-interface generator 108; a first micro-interface generator 104 connected to the propylene inlet 103 for breaking propylene into micro-bubbles; a second micro-interfacial generator 108 is coupled to the syngas inlet 102 for breaking up the syngas into micro-bubbles. In this embodiment, the first micro-interface generator 104 is a hydraulic micro-interface generator, and the second micro-interface generator 108 is a pneumatic micro-interface generator.
Wherein the first micro-interface generator 104 is disposed directly above the second micro-interface generator 108 and the outlet of the first micro-interface generator 104 is opposite to the outlet of the second micro-interface generator 108. The two micro-interface generators are opposite, so that a hedging effect can be achieved, and gas distribution is promoted.
At the outlet of the first micro-interfacial surface generator 104, a screen 105 is arranged, and at the outlet of the second micro-interfacial surface generator 108, a guide disc 107 is arranged. The guide disc 107 is conical; a plurality of guide holes are uniformly distributed on the guide disc 107. Specifically, the guide curve of the guide disk 107 is any one of a hyperbolic curve, a parabolic curve, a two-segment broken line, and a logarithmic curve. During the in-service use, can also increase the guiding hole along the direction diameter of keeping away from the feed inlet in proper order to make the direction diverse of guiding hole, when the microbubble passed through direction disc 107, evenly distributed in the solvent behind the guiding hole distribution.
In the present embodiment, an injector 106 for injecting a catalyst is installed on the inner sidewall of the reactor 10, and an injection port of the injector 106 faces between the first micro-interface generator 104 and the second micro-interface generator 108; a catalyst reservoir 190 is connected to the injector 106.
As shown in fig. 2, the ejector 106 is semicircular, the ejection heads 109 are connected to the ejector 106, and the ejection heads 109 are uniformly distributed on the semicircular surface of the ejector 106. The catalyst is dispersed in the reactor 10 by spraying, and the reaction effect can be improved.
In addition, the top of the reactor 10 is connected with a first condenser 180; the non-condensable gas outlet of the first condenser 180 is connected to the combustion system 170, and the condensate outlet of the first condenser 180 is connected to the reactor 10. The tail gas at the top of the reactor 10 is condensed by the first condenser 180, high boiling point substances such as n-butyraldehyde/isobutyraldehyde and the like are condensed into liquid and returned to the reactor 10, and noncondensable gases such as nitrogen, hydrogen, propane, carbon monoxide and the like enter the combustion system 170 to be combusted and removed.
During the reaction, the solvent is firstly introduced into the reactor 10 through the solvent inlet 101, and the liquid level of the solvent is higher than that of the first micro-interface generator 104. Propylene is dispersed into large bubbles through the pre-disperser 160 and then further dispersed into micron-sized micro-bubbles through the first micro-interface generator 104, synthetic gas is dispersed into large bubbles through the pre-disperser 160 and then further dispersed into micron-sized micro-bubbles through the second micro-interface generator 108, solutes provide a liquid phase medium for the dispersion and the crushing of the propylene and the synthetic gas, and a catalyst is sprayed between the first micro-interface generator 104 and the second micro-interface generator 108 through the sprayer 106 to catalyze the carbonylation reaction of the propylene. Demisting the reaction product by a demister 20, condensing the demisted reaction product by a second condenser 30, feeding the condensed demisted reaction product into a gas-liquid separator 40, carrying out gas-liquid separation, allowing the gas-phase material flow to flow back into the reactor 10 to continuously participate in the reaction, allowing one part of the liquid-phase material flow to enter an isomer separation tower 70, cooling the other part of the liquid-phase material flow to about 80 ℃ by a third condenser 60, and returning the cooled part of the liquid-phase material flow to a first micro-interface generator 104 in the reactor 10 to continuously participate. The isomerate separating column 70 separates the products, and the separated n-butyraldehyde is rectified in the rectifying column 90 and then flows into the n-butyraldehyde storage tank 110.
In a word, the micro-interface reaction system greatly reduces the reaction temperature and pressure required by propylene carbonylation, has low energy consumption, low cost, high safety, less side reaction and high n-butyraldehyde yield, and is worthy of wide popularization and application.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde comprising: the system comprises a solvent storage tank, a reactor, a gas-liquid separator, a propylene storage tank, a carbon monoxide storage tank, a hydrogen storage tank, a propylene pipeline and a synthesis gas pipeline; the side wall of the reactor is sequentially provided with a propylene inlet and a synthesis gas inlet from top to bottom; the bottom of the reactor is provided with a solvent inlet which is connected with the solvent storage tank; a demister is arranged between the reactor and the gas-liquid separator; demisting the product in the reactor by the demister, and then flowing into the gas-liquid separator for gas-liquid separation;
a first micro-interface generator and a second micro-interface generator are arranged in the reactor; the first micro-interface generator is connected with the propylene inlet and is used for dispersing and breaking propylene into micro-bubbles; the second micro-interface generator is connected with the synthesis gas inlet and is used for dispersing and breaking the synthesis gas into micro-bubbles;
the propylene inlet is connected with the propylene storage tank through the propylene pipeline; the carbon monoxide storage tank and the hydrogen storage tank are connected in parallel, and are both connected with the synthesis gas inlet through the synthesis gas pipeline; the propylene pipeline and the synthesis gas pipeline are respectively provided with a pre-disperser used for pre-dispersing and crushing gas into bubbles; the pre-disperser comprises a gas phase main path and a liquid phase branch path; the liquid phase branch is connected with the solvent storage tank, and the solvent in the solvent storage tank enters the gas phase main path through the liquid phase branch and is mixed with the gas in the gas phase main path to form bubbles;
an ejector for ejecting catalyst is arranged on the inner side wall of the reactor, and an ejection port of the ejector faces to a position between the first micro interface generator and the second micro interface generator; the ejector is connected with a catalyst storage tank.
2. The micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to claim 1, wherein said first micro-interfacial generator is positioned directly above said second micro-interfacial generator and wherein said first micro-interfacial generator is opposite to the outlet of said second micro-interfacial generator.
3. The micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to claim 1, wherein the first micro-interfacial generator is a hydraulic micro-interfacial generator and the second micro-interfacial generator is a pneumatic micro-interfacial generator.
4. The micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to claim 1, wherein a screen is provided at the outlet of the first micro-interfacial generator, and a guide disk is provided at the outlet of the second micro-interfacial generator.
5. The micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to claim 4 wherein said pilot disc is conical; a plurality of guide holes are uniformly distributed on the guide disc.
6. The micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to claim 1, wherein the sparger is semi-circular in shape and is connected with spray heads that are uniformly distributed on the semi-circular surface of the sparger.
7. The micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to claim 1, wherein a second condenser is disposed between the demister and the vapor-liquid separator; and a material outlet of the gas-liquid separator is sequentially connected with an isomerate separating tower, a rectifying tower and a n-butyl aldehyde storage tank.
8. The micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to claim 1 wherein a first condenser is connected to the top of the reactor; and a non-condensable gas outlet of the first condenser is connected with a combustion system, and a condensate outlet of the first condenser is connected with the reactor.
9. A reaction process using the micro-interfacial reaction system for the carbonylation of propylene to butyraldehyde according to any one of claims 1 to 8, comprising the steps of:
respectively dispersing and crushing propylene and synthesis gas through a micro interface, mixing the propylene and the synthesis gas with a catalyst, carrying out hydroxyl synthesis reaction, carrying out defoaming condensation gas-liquid separation to obtain a crude product, separating n-butyl aldehyde and iso-butyl aldehyde from the crude product, and carrying out rectification and purification to obtain the n-butyl aldehyde.
10. The reaction method of claim 9, wherein the hydroxyl synthesis reaction temperature is 85 to 90 ℃ and the pressure is 1.1 to 1.8 MPa; preferably, the catalyst is a rhodium catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113578203A (en) * | 2021-07-16 | 2021-11-02 | 南京延长反应技术研究院有限公司 | System and method for preparing DMC (dimethyl carbonate) through methanol carbonylation |
| CN113680286A (en) * | 2021-08-31 | 2021-11-23 | 南京延长反应技术研究院有限公司 | Propylene carbonylation reaction system and method with recyclable catalyst |
| CN114618396A (en) * | 2022-03-21 | 2022-06-14 | 南京诚志清洁能源有限公司 | Propylene carbonylation reaction device and method |
| WO2023077843A1 (en) | 2021-11-08 | 2023-05-11 | 南京延长反应技术研究院有限公司 | Method for evaluating enhancement degree of micro-interface reaction for preparing butyraldehyde by means of hydroformylation of propylene |
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2021
- 2021-04-01 CN CN202110354304.8A patent/CN113061080A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578203A (en) * | 2021-07-16 | 2021-11-02 | 南京延长反应技术研究院有限公司 | System and method for preparing DMC (dimethyl carbonate) through methanol carbonylation |
| CN113680286A (en) * | 2021-08-31 | 2021-11-23 | 南京延长反应技术研究院有限公司 | Propylene carbonylation reaction system and method with recyclable catalyst |
| CN113680286B (en) * | 2021-08-31 | 2023-08-01 | 南京延长反应技术研究院有限公司 | Propylene carbonylation reaction system and method with recyclable catalyst |
| WO2023077843A1 (en) | 2021-11-08 | 2023-05-11 | 南京延长反应技术研究院有限公司 | Method for evaluating enhancement degree of micro-interface reaction for preparing butyraldehyde by means of hydroformylation of propylene |
| CN114618396A (en) * | 2022-03-21 | 2022-06-14 | 南京诚志清洁能源有限公司 | Propylene carbonylation reaction device and method |
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